Catalyst carrier, catalyst and process for producing the same

ABSTRACT

The present invention provides a catalyst carrier having excellent durability and capable of attaining high catalytic ability without increasing the specific surface area thereof, and a catalyst obtainable by using the catalyst carrier. The catalyst carrier of the present invention comprises a metal oxycarbonitride, preferably the metal contained in the metal oxycarbonitride comprises at least one selected from the group consisting of niobium, tin, indium, platinum, tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold, silver, iridium, palladium, yttrium, ruthenium, lanthanum, cerium, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and nickel. Moreover, the catalyst of the present invention comprises the catalyst carrier and a catalyst metal supported on the catalyst carrier.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation application of U.S. application Ser.No. 12/918,456 filed Aug. 19, 2010, which is a 371 of PCT InternationalApplication No. PCT/JP2009/052234 filed Feb. 10, 2009, which claimsbenefit of Japanese Patent Application No. 2008-038969 filed Feb. 20,2008. The above-noted applications are incorporated herein by referenceto their entirety.

The present invention relates to a catalyst carrier, a catalyst and aprocess for producing the catalyst, more specifically, it relates to acatalyst carrier comprising a metal oxycarbonitride, a catalystobtainable using the carrier and a process for producing the catalyst.

TECHNICAL BACKGROUND

Fuel cells are classified into various types in accordance with the kindof an electrolyte or the kind of an electrode. Typical examples are analkali type, a phosphoric acid type, a molten carbonate type, a solidelectrolyte type and a solid polymer type. Among them, the solid polymertype fuel cell capable of operating at a temperature of from a lowtemperature of about −40° C. to about 120° C. has been in the spotlight,and recently, the development and practical use thereof has beenadvanced as power sources having low environmental pollution used inautomobiles. Driving sources for cars and fixed electric sources havebeen studied as the use of the solid polymer type fuel cell. In order tothe cells to these uses, they are demanded to have durability for a longperiod of time.

The solid polymer type fuel cell has a form such that a polymer solidelectrolyte is sandwiched between an anode and a cathode, a fuel is fedto the anode while oxygen or air is fed to the cathode and therebyoxygen is reduced in the cathode to produce electricity. Hydrogen,methanol or the like is mainly used as the fuel.

Conventionally, in order to enhance the reaction rate of a fuel cell andenhance the energy exchange efficiency of a fuel cell, acatalyst-containing layer (hereinafter sometimes referred to a catalystlayer for fuel cells) is provided on the cathode (air electrode) surfaceor the anode (fuel electrode) surface of a fuel cell.

As this catalyst, noble metals are generally used and further among thenoble metals, platinum, which is stable at a higher electric potentialand has high activity, has been used. As the carrier, which supports thecatalyst metal, carbon has been used conventionally.

The catalytic ability of the carrier carbon can be enhanced only byincreasing the specific surface area thereof. Therefore, the particlediameter of the carrier carbon needs to be diminished. However, thediminishing of the particle diameter of the carrier carbon has thetechnical limits. The catalyst obtainable by using the carrier carboncannot secure sufficient catalytic ability.

Furthermore, the carbon has low heat resistance, and the carrier carboncorrodes and disappears with running the reaction in a fuel cell, so thecatalyst metal particles such as Pt and the like which are supported onthe carrier carbon are liberated from the carrier to cause a phenomenonsuch that the catalyst metal is flocculated. As a result, the effectivearea is lowered and the cell ability is also lowered.

In order to solve this problem, Patent document 1 discloses an electrodecatalyst layer of a fuel cell which corrosion resistance is enhanced bythermally treating a carrier carbon at a high temperature (PatentDocument 1).

However, there is no change in the structure that platinum and the likeare directly supported on the carbon carrier, which suffers corrosionand disappearance in the noble electric potential environment, so thecorrosion resistance is not vastly improved even by the above technique.

-   Patent Document 1: JP-A-2002-273224

DISCLOSURE OF INVENTION Subject to be Solved by the Invention

The present invention is intended to solve the above problems associatedwith the prior arts, and it is an object of the present invention toprovide a catalyst carrier having excellent durability and capable ofexerting high catalytic ability without increasing the specific surfacearea, it is another object of the present invention to provide acatalyst obtainable by using the catalyst carrier and a process forproducing the catalyst.

Means for Solving the Subject

The present inventors have been earnestly studied in order to solve theabove problems associated with prior arts, and found that a catalystcarrier comprising a metal oxycarbonitride has high durability and canexert high catalytic ability without increasing the specific surfacearea thereof. As a result, the present invention has been accomplished.

The present invention relates to the following characteristics (1) to(9) for example.

(1) The catalyst carrier of the present invention comprises a metaloxycarbonitride.

(2) The catalyst carrier according to (1) is characterized in that themetal of the metal oxycarbonitride is at least one metal selected fromthe group consisting of niobium, tin, indium, platinum, tantalum,zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium,titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold,silver, iridium, palladium, yttrium, ruthenium, lanthanum, praseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and nickel.

(3) The catalyst carrier according to (1) is characterized in that themetal of the metal oxycarbonitride is niobium.

(4) The catalyst carrier according to (2) is characterized in that themetal oxycarbonitride has a composition represented by MC_(x)N_(y)O_(z)wherein M is at least one metal selected from the group consisting ofniobium, tin, indium, platinum, tantalum, zirconium, copper, iron,tungsten, chromium, molybdenum, hafnium, titanium, vanadium, cobalt,manganese, cerium, mercury, plutonium, gold, silver, iridium, palladium,yttrium, ruthenium, lanthanum, praseodymium, neodymium, promethium,samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium,thulium, ytterbium, lutetium, and nickel, x, y and z are each aproportion of each atomic number and satisfy 0.01≦x≦2, 0.01≦y≦2,0.01≦z≦3 and x+y+z≦5.

(5) The catalyst of the present invention comprises a catalyst carrieras described in any one of (1) to (4) and a catalyst metal supported onthe catalyst carrier.

(6) The catalyst according to (5) is characterized in that the catalystmetal is at least one selected from the group consisting of Pt, Ir, Ag,Pd and Ru.

(7) The catalyst according to (5) or (6) is characterized in that thecatalyst metal comprises metal particles having an average particlediameter of 1 to 20 nm.

(8) The catalyst according to any one of (5) to (7) is characterized inthat it is used for fuel cells.

(9) A process for producing a catalyst capable of supporting a catalystmetal on a catalyst carrier as described in any one of (1) to (4).

(10) The process for producing the catalyst according to (9) ischaracterized in that the catalyst metal is supported using a precursorof the catalyst.

Effect of the Invention

The catalyst carrier of the present invention has excellent heatresistance and can exert high catalytic ability without increasing thespecific surface area.

BRIEF DESCRIPTION OF THE DRAWING

FIG. 1 is a powder X-ray diffraction spectrum of a catalyst carrier (1).

FIG. 2 is a powder X-ray diffraction spectrum of a catalyst (1) inExample 1.

FIG. 3 is a graph showing an evaluation on oxygen reducing ability of anelectrode (1) for fuel cells in Example 1.

FIG. 4 is an X-ray diffraction spectrum of a powder of a catalyst (2) inExample 2.

FIG. 5 is a graph showing an evaluation on oxygen reducing ability of anelectrode (2) for fuel cells in Example 2.

FIG. 6 is a graph showing an evaluation on oxygen reducing ability of anelectrode (3) for fuel cells in Comparative Example 1.

FIG. 7 is a graph showing an evaluation on oxygen reducing ability of anelectrode (4) for fuel cells in Comparative Example 2.

FIG. 8 is a view showing the graphs in the evaluation on oxygen reducingability of the electrodes (2) for fuel cells in Examples 1 and 2 andComparative Examples 1 and 2 together.

FIG. 9 is a view showing a comparison on current density at 0.85 V ineach of Examples 1 and 2 and Comparative Examples 1 and 2.

FIG. 10 is a SEM photograph of a carrier supporting platinum thatplatinum is supported on a niobium oxycarbonitride carrier in Example 1.

FIG. 11 is a SEM photograph of a carrier supporting platinum thatplatinum is supported on a carbon carrier in Comparative Example 1.

FIG. 12 is a powder X-ray diffraction spectrum of a catalyst (5) inExample 3.

FIG. 13 is a graph showing an evaluation on oxygen reducing ability ofan electrode (5) for fuel cells in Example 3.

FIG. 14 is a powder X-ray diffraction spectrum of a catalyst (6) inExample 4.

FIG. 15 is a graph showing an evaluation on oxygen reducing ability ofan electrode (6) for fuel cells in Example 4.

FIG. 16 is a powder X-ray diffraction spectrum of a catalyst (7) inExample 5.

FIG. 17 is a graph showing an evaluation on oxygen reducing ability ofan electrode (7) for fuel cells in Example 5.

BEST EMBODIMENT FOR CARRYING OUT THE INVENTION <Catalyst Carrier>

The catalyst carrier of the present invention comprises a metaloxycarbonitride.

The metal in the metal oxycarbonitride is preferably at least one metalselected from the group consisting of niobium, tin, indium, platinum,tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum,hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury,plutonium, gold, silver, iridium, palladium, yttrium, ruthenium,lanthanum, praseodymium, neodymium, promethium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium and nickel (hereinafter optionally referred to “metal M”). Thecatalyst carrier made from the oxycarbonitride of the metal particularlyhas excellent durability and can exert high catalytic ability withoutincreasing the specific surface area.

Among these metals, niobium is particularly preferred. Furthermore, itis preferred to employ the combined use of niobium and at least onemetal selected from the group consisting of tin, indium, platinum,tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum,hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury,plutonium, gold, silver, iridium, palladium, yttrium, ruthenium,lanthanum, praseodymium, neodymium, promethium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium, and nickel (hereinafter optionally referred to “metal M′”).

The metal oxycarbonitride has a composition represented byMC_(x)N_(y)O_(z). In the formula, M is at least one metal selected fromthe group consisting of niobium, tin, indium, platinum, tantalum,zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium,titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold,silver, iridium, palladium, yttrium, ruthenium, lanthanum, praseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and nickel,x, y and z are each a proportion of each atomic number and satisfy0.01≦x≦2, 0.01≦y≦2, 0.01≦z≦3 and x+y+z≦5.

When the metal of the metal oxycarbonitride is niobium, the metaloxycarbonitride has a composition represented by NbC_(x)N_(y)O_(z).

In the formula, x, y and z are each a proportion of each atomic numberand satisfy 0.01≦x≦2, 0.01≦y≦2, 0.01≦z≦3 and x+y+z≦5.

When the metal of the metal oxycarbonitride is niobium and at least onemetal selected from the group consisting of tin, indium, platinum,tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum,hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury,plutonium, gold, silver, iridium, palladium, yttrium, ruthenium,lanthanum, praseodymium, neodymium, promethium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium and nickel, the metal oxycarbonitride has a compositionrepresented by Nb_(a)M′_(b)C_(x)N_(y)O_(z). In the formula, M′ is atleast one metal selected from the group consisting of tin, indium,platinum, tantalum, zirconium, copper, iron, tungsten, chromium,molybdenum, hafnium, titanium, vanadium, cobalt, manganese, cerium,mercury, plutonium, gold, silver, iridium, palladium, yttrium,ruthenium, lanthanum, praseodymium, neodymium, promethium, samarium,europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium,ytterbium, lutetium and nickel, a, b, x, y and z are each a proportionof each atomic number and when a+b=1, they satisfy 0.01≦a<1, 0<b≦0.99,0.01≦x≦2, 0.01≦y≦2, 0.01≦z≦3 and x+y+z≦5.

Each element proportion is preferably in the above range because theoxygen reducing potential tends to be higher.

The catalyst carrier of the present invention has an average particlediameter of, for example, 10 to 2000 nm, preferably 10 to 1000 nm. Theaverage particle diameter is a value obtainable by the BET method. Evenif the catalyst carrier of the present invention has a particle diameterin the above range, the catalyst prepared using the catalyst carrier hassufficiently high catalytic ability. When carbon is used as the catalystcarrier, the average particle diameter needs to be about 10 to 100 nmfor increasing the specific surface area in order to attain the samecatalytic ability. As described above, the catalyst carrier made fromthe metal oxycarbonitride of the present invention can securesufficiently high catalytic ability without decreasing the particlediameter.

In the catalyst carrier of the present invention, it is preferred thattwo or more peaks be observed in the diffraction line at a diffractionangle 2θ between 33° to 43° by a powder X-ray diffraction method (Cu—Kαray).

The peak in the diffraction pattern is a peak obtainable by a specificdiffraction angle and specific diffraction intensity when a specimen(crystal form) is irradiated with an X-ray at various angles.

In the present invention, a signal detectable by a ratio (S/N) of signal(S) to noise (N) of not less than 2 is regarded to one peak in thediffraction line.

Herein, the noise (N) is a width of a base line.

As the X-ray diffraction method, for example, a powder X-ray analysisdevice: Rigaku RAD-RX can be used. The measurement can be carried out inthe following measuring conditions that X-ray output (Cu—Kα) is 50 kV,180 mA, the scanning axis is θ/2θ, the measuring range (2θ) is 10° to89.98°, the measuring mode is FT, the reading width is 0.02°, thesampling time is 0.70 sec, DS, SS and RS are 0.5°, 0.5° and 0.15 mmrespectively and the goniometer radius is 185 mm.

As the process for producing the catalyst carrier, which is notparticularly limited, for example, there is a process including a stepof preparing a metal oxycarbonitride by thermally treating a metalcarbon nitride in an inert gas containing oxygen.

When the catalyst carrier comprises a metal oxycarbonitride containing ametal M, there is a process including a step of preparing a metaloxycarbonitride containing a metal M by thermally treating a metalcarbon nitride containing a metal M in an inert gas containing oxygen.

When the catalyst carrier comprises a metal oxycarbonitride containingniobium and a metal M′, there is a process including a step of preparinga metal oxycarbonitride containing niobium and a metal M′ by thermallytreating a metal carbon nitride containing niobium and a metal M′ in aninert gas containing oxygen.

Examples of the process for preparing the metal carbon nitride mayinclude (i) a process for producing the metal carbon nitride bythermally treating a mixture of a metal oxide and carbon in a nitrogenatmosphere and (ii) a process for producing the metal carbon nitride bythermally treating a mixture of a metal carbide, a metal oxide and ametal nitride in a nitrogen atmosphere.

Examples of the process for preparing the metal carbon nitridecontaining a metal M may include (I) a process for producing the metalcarbon nitride by thermally treating a mixture of an oxide of the metalM and carbon in a nitrogen atmosphere, (II) a process for producing themetal carbon nitride by thermally treating a mixture of an oxide of themetal M, a carbide of the metal M and a nitride of the metal M in anitrogen atmosphere and the like, and (III) a process for producing themetal carbon nitride by thermally treating a compound containing themetal M in a nitrogen atmosphere and the like.

Examples of the process for preparing the metal carbon nitridecontaining niobium and a metal M′ may include (I′) a process forproducing the metal carbon nitride by thermally treating a mixture of anoxide of the metal M′, niobium oxide and carbon in a nitrogenatmosphere, (II′) a process for producing the metal carbon nitride bythermally treating a mixture of an oxide of the metal M′, niobiumcarbide and a niobium nitride in a nitrogen atmosphere and the like,(III′) a process for producing the metal carbon nitride by thermallytreating a mixture of an oxide of the metal M′, niobium carbide, niobiumnitride and niobium oxide in a nitrogen atmosphere and the like, and(IV′) a process for producing the metal carbon nitride by thermallytreating a mixture of a compound containing the metal M′ and a compoundcontaining niobium in a nitrogen atmosphere and the like. However, theproduction process is not limited to these processes.

The process for producing the metal carbon nitride which metal is ametal M or which metals are niobium and a metal M′ will be describedbelow. The production of the metal oxycarbonitride which metal isniobium, zirconium, titanium or the like can be carried out inaccordance with this production process.

(Production Process of the Metal Carbon Nitride)

<Production Process of the Metal Oxycarbonitride which Metal is a MetalM>

[Production Process (I)]

The production process (I) is a process for producing the metal carbonnitride by thermally treating the mixture of the oxide of the metal Mand carbon in a nitrogen atmosphere.

In producing the metal carbon nitride, the heat treatment is carried outat a temperature of 600 to 1800° C., preferably 800 to 1600° C. Thetemperature of the heat treatment is preferably in the above rangebecause the crystallinity and the uniformity are good. When thetemperature of the heat treatment is lower than 600° C., thecrystallinity tends to be inferior and the uniformity also tends to beinferior, while when it is higher than 1800° C., sintering tends to becaused.

Examples of the oxide of the metal M which is a raw material may includeniobium oxide, tin oxide, indium oxide, platinum oxide, tantalum oxide,zirconium oxide, copper oxide, iron oxide, tungsten oxide, chromiumoxide, molybdenum oxide, hafnium oxide, titanium oxide, vanadium oxide,cobalt oxide, manganese oxide, cerium oxide, mercury oxide, plutoniumoxide, gold oxide, silver oxide, iridium oxide, palladium oxide, yttriumoxide, ruthenium oxide, lanthanum oxide, praseodymium oxide, neodymiumoxide, promethium oxide, samarium oxide, europium oxide, gadoliniumoxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide,thulium oxide, ytterbium oxide, lutetium oxide and nickel oxide. It ispossible to use at least one of them as the oxide of the metal M.

Examples of the raw material carbon may include carbon, carbon black,graphite, plumbago, active carbon, carbon nano tube, carbon nano fiber,carbon nano horn and fullerene. The carbon powder preferably has a smallparticle diameter, because it has a larger specific surface area andthereby is easily reacted with the oxide. For example, carbon black(specific surface area: 100 to 300 m²/g, XC-72 manufactured by CabotCorporation) is preferably used.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the oxide of the metal M and carbon in an inert gas containingoxygen has a high starting potential for oxygen reduction and activity.

Controlling the mixing amount (molar ratio) of the oxide of the metal Mand carbon, it is possible to prepare the appropriate metal carbonnitride.

In the mixing amount (molar ratio), the carbon is contained in an amountof usually 1 to 10 mol, preferably 2 to 6 mol per 1 mol of the metal M.Using the metal carbon nitride prepared by the mixing ratio in the aboverange, it is possible to prepare the metal oxycarbonitride capable ofpreparing the active catalyst having a high starting potential foroxygen reduction. Furthermore, using the metal carbon nitride preparedby the mixing ratio in the above range, it is possible to easily preparethe metal oxycarbonitride (Nb_(a)M_(b)C_(x)N_(y)O_(z)) in which theatomic number ratio (a, b, x, y and z) and x+y+z are appropriate.

[Production Process (II)]

The production process (II) is a process for producing the metal carbonnitride by thermally treating the mixture of an oxide of the metal M, acarbide of the metal M and a nitride of the metal M in a nitrogenatmosphere and the like.

In producing the metal carbon nitride, the heat treatment is carried outat the same temperature as that in the production process (I).

Examples of the oxide of the metal M, which is a raw material, mayinclude the same oxides of the metal M as those described in theproduction process (I).

Examples of the carbide of the metal M which is a raw material mayinclude niobium carbide, tin carbide, indium carbide, platinum carbide,tantalum carbide, zirconium carbide, copper carbide, iron carbide,tungsten carbide, chromium carbide, molybdenum carbide, hafnium carbide,titanium carbide, vanadium carbide, cobalt carbide, manganese carbide,cerium carbide, mercury carbide, plutonium carbide, gold carbide, silvercarbide, iridium carbide, palladium carbide, yttrium carbide, rutheniumcarbide, lanthanum carbide, praseodymium carbide, neodymium carbide,promethium carbide, samarium carbide, europium carbide, gadoliniumcarbide, terbium carbide, dysprosium carbide, holmium carbide, erbiumcarbide, thulium carbide, ytterbium carbide, lutetium carbide and nickelcarbide. It is possible to use at least one of them as the carbide ofthe metal M.

Examples of the nitride of the metal M which is a raw material mayinclude niobium nitride, tin nitride, indium nitride, platinum nitride,tantalum nitride, zirconium nitride, copper nitride, iron nitride,tungsten nitride, chromium nitride, molybdenum nitride, hafnium nitride,titanium nitride, vanadium nitride, cobalt nitride, manganese nitride,cerium nitride, mercury nitride, plutonium nitride, gold nitride, silvernitride, iridium nitride, palladium nitride, yttrium nitride, rutheniumnitride, lanthanum nitride, praseodymium nitride, neodymium nitride,promethium nitride, samarium nitride, europium nitride, gadoliniumnitride, terbium nitride, dysprosium nitride, holmium nitride, erbiumnitride, thulium nitride, ytterbium nitride, lutetium nitride and nickelnitride. It is possible to use at least one of them as the nitride ofthe metal M.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the oxide of the metal M, the carbide of the metal M and thenitride of the metal M in an inert gas containing oxygen has a highstarting potential for oxygen reduction and activity.

Controlling the mixing amount (molar ratio) of the oxide of the metal M,the carbide of the metal M and the nitride of the metal M, it ispossible to prepare the appropriate metal carbon nitride. In the mixingamount (molar ratio), usually the carbide of the metal M is contained inan amount of 0.01 to 500 mol, the oxide of the metal M is contained inan amount of 0.01 to 50 mol per 1 mol of the nitride of the metal M,preferably the carbide of the metal M is contained in an amount of 0.1to 300 mol, the oxide of the metal M is contained in an amount of 0.01to 30 mol per 1 mol of the nitride of the metal M. Using the metalcarbon nitride prepared by the mixing ratio in the above range, it ispossible to prepare the metal oxycarbonitride capable of preparing theactive catalyst having a high starting potential for oxygen reduction.Furthermore, using the metal carbon nitride prepared by the mixing ratioin the above range, it is possible to easily prepare the metaloxycarbonitride (Nb_(a)M_(b)C_(x)N_(y)O_(z)) in which the atomic numberratio (a, b, x, y and z) and x+y+z are appropriate.

Moreover, even if using the mixture of only the carbide of the metal Mand the nitride of the metal M, the metal carbon nitride can be preparedin the above manner.

[Production Process (III)]

The production process (III) is a process for producing the metal carbonnitride by thermally treating the compound containing the metal M in anitrogen atmosphere and the like.

In producing the metal carbon nitride, the heat treatment is carried outat the same temperature as that in the production process (I).

Examples of the compound containing the metal M which is a raw materialmay include organic acid salts, carbonic acid salts, chlorides, organiccomplexes, carbides and nitrides of niobium, tin, indium, platinum,tantalum, zirconium, copper, iron, tungsten, chromium, molybdenum,hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury,plutonium, gold, silver, iridium, palladium, yttrium, ruthenium,lanthanum, praseodymium, neodymium, promethium, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium and nickel. It is possible to use at least one of them as thecompound containing the metal M.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the compound of the metal M in an inert gas containing oxygen has ahigh starting potential for oxygen reduction and activity.

Using the mixture only containing the compound containing the metal Mother than the carbide and nitride, the carbide of the metal M and thenitride of the metal M, it is possible to prepare the metal carbonnitride similarly in the above manner.

<Production Process of the Metal Oxycarbonitride that the Metals areNiobium and the Metal M>

[Production Process (I′)]

The production process (I′) is a process for producing the metal carbonnitride by thermally treating the mixture of the oxide of the metal M′,niobium oxide and carbon in a nitrogen atmosphere.

In producing the metal carbon nitride, the heat treatment is carried outat a temperature of 600 to 1800° C., preferably 800 to 1600° C. Thetemperature of the heat treatment is preferably in the above rangebecause the crystallinity and the uniformity are good. When thetemperature of the heat treatment is lower than 600° C., thecrystallinity is inferior and the uniformity also is inferior, whilewhen it is higher than 1800° C., sintering is easily caused.

Examples of the oxide of the metal M′ which is a raw material mayinclude tin oxide, indium oxide, platinum oxide, tantalum oxide,zirconium oxide, copper oxide, iron oxide, tungsten oxide, chromiumoxide, molybdenum oxide, hafnium oxide, titanium oxide, vanadium oxide,cobalt oxide, manganese oxide, cerium oxide, mercury oxide, plutoniumoxide, gold oxide, silver oxide, iridium oxide, palladium oxide, yttriumoxide, ruthenium oxide, lanthanum oxide, praseodymium oxide, neodymiumoxide, promethium oxide, samarium oxide, europium oxide, gadoliniumoxide, terbium oxide, dysprosium oxide, holmium oxide, erbium oxide,thulium oxide, ytterbium oxide, lutetium oxide and nickel oxide. It ispossible to use at least one of them as the oxide of the metal M′.

Examples of the niobium oxide, which is a raw material, may include NbO,NbO₂ and Nb₂O₅.

Examples of the raw material carbon may include carbon, carbon black,graphite, plumbago, active carbon, carbon nano tube, carbon nano fiber,carbon nano horn and fullerene. The carbon powder preferably has a smallparticle diameter, because it has a larger specific surface area andthereby is easily reacted with the oxide. For example, carbon black(specific surface area: 100 to 300 m²/g, XC-72 manufactured by CabotCorporation) is preferably used.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the oxide of the metal M′, niobium oxide and carbon in an inert gascontaining oxygen has a high starting potential for oxygen reduction andactivity.

Controlling the mixing amount (molar ratio) of the oxide of the metalM′, niobium oxide and carbon, it is possible to prepare the appropriatemetal carbon nitride.

In the mixing amount (molar ratio), the oxide of the metal M′ iscontained in an amount of 0.005 to 200 mol, and the carbon is containedin an amount of usually 1 to 1000 mol per 1 mol of niobium oxide,preferably the oxide of the metal M′ is contained in an amount of 0.01to 200 mol, and the carbon is contained in an amount of usually 2 to 600mol per 1 mol of niobium oxide. Using the metal carbon nitride preparedby the mixing ratio in the above range, it is possible to prepare themetal oxycarbonitride capable of preparing the active catalyst having ahigh starting potential for oxygen reduction. Furthermore, using themetal carbon nitride prepared by the mixing ratio in the above range, itis possible to easily prepare the metal oxycarbonitride(Nb_(a)M_(b)C_(x)N_(y)O_(z)) in which the atomic number ratio (a, b, x,y and z) and x+y+z are appropriate.

[Production Process (II′)]

The production process (II′) is a process for producing the metal carbonnitride by thermally treating the mixture of an oxide of the metal M′, aniobium carbide and a niobium nitride in a nitrogen atmosphere and thelike.

In producing the metal carbon nitride, the heat treatment is carried outat the same temperature as that in the production process (I′).

Examples of the oxide of the metal M′, which is a raw material, mayinclude the same oxides of the metal M′ as those described in theproduction process (I′).

Examples of the niobium carbide may include NbC and the like.

Examples of the niobium nitride may include NbN and the like.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the oxide of the metal M′, the niobium carbide and the niobiumnitride in an inert gas containing oxygen has a high starting potentialfor oxygen reduction and activity.

Controlling the mixing amount (molar ratio) of the oxide of the metalM′, the niobium carbide and the niobium nitride, it is possible toprepare the appropriate metal carbon nitride. In the mixing amount(molar ratio), usually the niobium carbide is contained in an amount of0.01 to 500 mol and the oxide of the metal M′ is contained in an amountof 0.01 to 50 mol per 1 mol of the niobium nitride, preferably theniobium carbide is contained in an amount of 0.1 to 300 mol and theoxide of the metal M′ is contained in an amount of 0.02 to 30 mol per 1mol of the niobium nitride. Using the metal carbon nitride prepared bythe mixing ratio in the above range, it is possible to prepare the metaloxycarbonitride capable of preparing the active catalyst having a highstarting potential for oxygen reduction. Furthermore, using the metalcarbon nitride prepared by the mixing ratio in the above range, it ispossible to easily prepare the metal oxycarbonitride(Nb_(a)M_(b)C_(x)N_(y)O_(z)) in which the atomic number ratio (a, b, x,y and z) and x+y+z are appropriate.

[Production Process (III′)]

The production process (III′) is a process for producing the metalcarbon nitride by thermally treating the mixture of an oxide of themetal M′, niobium carbide, niobium nitride and niobium oxide in anitrogen atmosphere and the like.

In producing the metal carbon nitride, the heat treatment is carried outat the same temperature as that in the production process (I′).

Examples of the oxide of the metal M′, which is a raw material, mayinclude the same oxides of the metal M′ as those described in theproduction process (I′).

Examples of the niobium carbide may include NbC and the like.

Examples of the niobium nitride may include NbN and the like.

Examples of the niobium oxide may include NbO, NbO₂, Nb₂O₅ and the like.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the oxide of the metal M′, the niobium carbide, the niobium nitrideand the niobium oxide in an inert gas containing oxygen has a highstarting potential for oxygen reduction and activity.

Controlling the mixing amount (molar ratio) of the oxide of the metalM′, the niobium carbide, the niobium nitride and the niobium oxide, itis possible to prepare the appropriate metal carbon nitride. In themixing amount (molar ratio), usually the niobium carbide is contained inan amount of 0.01 to 500 mol, and the oxide of the metal M′ and theniobium oxide are contained in a total amount of 0.01 to 50 mol per 1mol of the niobium nitride, preferably the niobium carbide is containedin an amount of 0.1 to 300 mol and the oxide of the metal M′ and niobiumoxide are contained in a total amount of 0.02 to 30 mol per 1 mol of theniobium nitride. Using the metal carbon nitride prepared by the mixingratio in the above range, it is possible to prepare the metaloxycarbonitride capable of preparing the active catalyst having a highstarting potential for oxygen reduction. Furthermore, using the metalcarbon nitride prepared by the mixing ratio in the above range, it ispossible to easily prepare the metal oxycarbonitride(Nb_(a)M_(b)C_(x)N_(y)O_(z)) in which the atomic number ratio (a, b, x,y and z) and x+y+z are appropriate.

[Production Process (IV′)]

The production process (IV′) is a process for producing the metal carbonnitride by thermally treating the mixture of a compound containing themetal M′ and a compound containing niobium in a nitrogen atmosphere andthe like.

In producing the metal carbon nitride, the heat treatment is carried outat the same temperature as that in the production process (I′).

Examples of the compound containing the metal M′ which is a raw materialmay include organic acid salts, carbonic acid salts, chlorides, organiccomplexes, carbides and nitrides of tin, indium, platinum, tantalum,zirconium, copper, iron, tungsten, chromium, molybdenum, hafnium,titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold,silver, iridium, palladium, yttrium, ruthenium, lanthanum, praseodymium,neodymium, promethium, samarium, europium, gadolinium, terbium,dysprosium, holmium, erbium, thulium, ytterbium, lutetium and nickel. Itis possible to use at least one of them as the compound containing themetal M′.

Examples of the compound containing niobium may include organic acidsalts, carbonic acid salts, chlorides, organic complexes, carbides andnitrides of niobium. It is possible to use at least one of them as thecompound containing niobium.

Even if using the mixture of the compound containing the metal M′,niobium carbide and niobium nitride, it is possible to prepare the metalcarbon nitride in which the metals are niobium and the metal M in thesame manner as above.

The raw materials are not particularly limited. Even if any of the rawmaterials is used, the catalyst prepared from the metal oxycarbonitrideobtainable by thermally treating the metal carbon nitride obtainablefrom the compound containing the metal M′ and the compound containingniobium in an inert gas containing oxygen has a high starting potentialfor oxygen reduction and activity.

Controlling the mixing amount (molar ratio) of the compound containingthe metal M′ and the compound containing niobium, it is possible toprepare the appropriate metal carbon nitride. In the mixing amount(molar ratio), usually the compound containing niobium is contained inan amount of 0.005 to 500 mol per 1 mol of the compound containing themetal M′, preferably the compound containing niobium is contained in anamount of from 0.01 to 300 mol per 1 mol of the compound containing themetal M′. Using the metal carbon nitride prepared by the mixing ratio inthe above range, it is possible to prepare the metal oxycarbonitridecapable of preparing the active catalyst having a high startingpotential for oxygen reduction. Furthermore, using the metal carbonnitride prepared by the mixing ratio in the above range, it is possibleto easily prepare the metal oxycarbonitride (Nb_(a)M_(b)C_(x)N_(y)O_(z))in which the atomic number ratio (a, b, x, y and z) and x+y+z areappropriate.

(Production Process of Metal Oxycarbonitride)

Next, the process for preparing the metal oxycarbonitride by thermallytreating the metal carbon nitride prepared in each of the productionprocesses (I) to (III) and (I′) to (IV′) in an inert gas containingoxygen will be described.

Examples of the inert gas may include nitrogen, helium gas, neon gas,argon gas, krypton gas, xenon gas and radon gas. The nitrogen gas andargon gas are particularly preferred in the viewpoint of easyacquisition thereof.

The oxygen concentration in the process, which depends on the heattreating time and the heat treating temperature, is preferably 0.1 to10% by volume, furthermore preferably 0.5 to 5% by volume. The oxygenconcentration is preferably in the above range because a uniformoxycarbonitride is formed. When the oxygen concentration is less than0.1% by volume, oxidation conditions tend to be immature, while when itis over 10% by volume, oxidation tends to proceed excessively.

The inert gas preferably contains hydrogen gas in an amount of not morethan 5% by volume. The amount of hydrogen gas contained is morepreferably 0.01 to 4% by volume, furthermore preferably 0.1 to 4% byvolume. The % by volume used in the present invention is a value in astandard condition.

The temperature of the heat treatment in the process is usually 400 to1400° C., preferably 600 to 1200° C. The heat-treating temperature ispreferably in the above range because a uniform metal oxycarbonitride isformed. When the heat-treating temperature is lower than 400° C.,oxidation tends to not proceed, while when it is over 1400° C.,oxidation tends to proceed excessively and thereby the metaloxycarbonitride grows into crystals.

Examples of the heat treatment method in the process may include astanding method, a stirring method, a dropping method and a powdercapturing method.

The dropping method is a method, which comprises heating an inducingfurnace to a predetermined heat treating temperature while passing aninert gas containing a slight amount of oxygen into the furnace, keepingthermal balance at the temperature and then dropping a metal carbonnitride in a crucible that is in the heating zone of the furnace andthereby carrying out the heat treatment. The dropping method ispreferable because it is possible to depress the cohesion and growth ofthe metal carbon nitride particles at the bare minimum.

The powder capturing method is a method, which comprises making themetal carbon nitride into spray and thereby being floated in an inertgas atmosphere containing a slight amount of oxygen, capturing the metalcarbon nitride in a vertical tube-like furnace kept at a predeterminedtemperature for the heat treatment and thereby carrying out heattreatment.

In the dropping method, the time of the heat treatment for the metalcarbon nitride is usually 0.5 to 10 min, preferably 0.5 to 3 min. Thetime of the heat treatment is preferably in the above range because theuniform oxycarbonitride tends to be formed. When the time of the heattreatment is less than 0.5 min, the metal oxycarbonitride tends to bepartly formed, while when it is over 10 min, oxidation tends to proceedexcessively.

In the powder capturing method, the time of the heat treatment for themetal carbon nitride is usually 0.2 sec to 1 min, preferably 0.2 to 10sec. The time of the heat treatment is preferably in the above rangebecause the uniform oxycarbonitride tends to be formed. When the time ofthe heat treatment is less than 0.2 sec, the metal oxycarbonitride tendsto be partly formed, while when it is over 1 min, oxidation tends toproceed excessively. In the heat treatment using the tube-like furnace,the time of the heat treatment for the metal carbon nitride is usually0.1 to 10 hr, preferably 0.5 to 5 hr. The time of the heat treatment ispreferably in the above range because the uniform oxycarbonitride tendsto be formed. When the time of the heat treatment is less than 0.1 hr,the metal oxycarbonitride tends to be partly formed, while when it isover 10 hr, oxidation tends to proceed excessively.

When the catalyst is produced from the metal oxycarbonitride, the metaloxycarbonitride prepared in the above production process may be used asit is, or the resulting metal oxycarbonitride may be further pulverizedto prepare the finely powdery metal oxycarbonitride and the finelypowdery one may be used.

Examples of the method of pulverizing the metal oxycarbonitride mayinclude methods by a roll rotating mill, a ball mill, a medium stirringmill, a gas stream pulverizing machine, a mortar and a pulverizingvessel. The method using the gas stream pulverizing machine ispreferable in the viewpoint of making the metal oxycarbonitride intomore fine particles, while the method using the mortar is preferable inthe viewpoint of easily treating a small amount of the metaloxycarbonitride.

<Catalyst>

The catalyst of the present invention comprises the catalyst carrier andthe catalyst metal supported on the catalyst carrier.

Non-limiting examples of the metal catalyst may include known catalystmetals, such as Pt, Ir, Ag, Pd and Ru. These catalyst metals may be usedsingly or two or more may be used in combination. Among them, Pt ispreferable because of having high mass activity.

The catalyst metal supported on the catalyst carrier is usually aparticulate metal. The particulate metal has an average particlediameter of preferably 1 to 20 nm, more preferably 1 to 10 nm. Thisaverage particle diameter is a number determined by the BET method. Whenthe particulate metal has an average particle diameter in the aboverange, it has high catalyst activity.

In the catalyst of the present invention, the mass ratio of the catalystcarrier to the catalyst metal supported (catalyst carrier/catalystmetal) is in the range of 100/0.01 to 100/70, preferably 100/0.1 to100/60.

The catalyst of the present invention has a starting potential foroxygen reduction, as measured in according to the following measuringmethod (A), of preferably not less than 0.5 V (vs. NHE) on the basis ofa reversible hydrogen electrode.

Measuring Method (A):

The catalyst and carbon are fed to a solvent in such an amount that theamount of the catalyst dispersed in carbon, which is electronicconductive particles, is 1% by weight, and stirred with an ultrasonicwave to prepare a suspension. As the carbon, carbon black (specificsurface area: 100 to 300 m²/g) (for example, XC-72 manufactured by CabotCo.) is used and the catalyst and the carbon are dispersed in a weightratio of 95/5. Moreover, the solvent having a weight ratio of isopropylalcohol to water of 2/1 is used.

30 μl of the suspension is collected while applying an ultrasonic wave,and quickly dropped on a glassy carbon electrode (diameter: 5.2 mm) anddried at 120° C. for 1 hr. The catalyst-containing catalyst layer forfuel cells is formed on the glassy carbon electrode by the drying.

Next, Nafion® (5% Nafion solution (DE521) manufactured by DuPont Co.) isdiluted 10 times with pure water and 10 μl of the diluted Nafion isdropped on the above catalyst layer for fuel cells and dried at 120° C.for 1 hr.

Using the resulting electrode thus prepared, polarization is performedin an oxygen atmosphere and in a nitrogen atmosphere in a 0.5 mol/dm³sulfuric acid solution at a temperature of 30° C. with a reversiblehydrogen electrode in a sulfuric acid solution having the sameconcentration as a reference electrode at a potential scanning rate of 5mV/sec and thereby the current-potential curve is measured. In themeasurement, the potential at which the difference between the reducingcurrent at an oxygen atmosphere and the reducing current at a nitrogenatmosphere becomes not less than 0.2 mA/cm² is taken as a startingpotential for oxygen reduction.

When the starting potential for oxygen reduction is less than 0.7 V (vs.NHE), hydrogen peroxide sometimes generates in using the catalyst for acathode of fuel cells. The starting potential for oxygen reduction ispreferably not less than 0.85 V (vs. NHE) in order to reduce oxygenproperly. Moreover, the starting potential for oxygen reduction ispreferably higher, and does not have the upper limit particularly. Thetheoretical value is 1.23 V (vs. NHE).

The catalyst layer for fuel cells formed using the above catalystaccording to the present invention is preferably used in an acidicelectrolyte at a potential of not less than 0.4 V (vs. NHE). The upperlimit of the potential is determined by the stability of the electrode.The catalyst layer can be used at an upper limiting potential at whichoxygen is generated of about 1.23 V (vs. NHE).

When the potential is less than 0.4 V (vs. NHE), there is no problem inthe viewpoint of stability of the niobium oxycarbonitride, but oxygencannot be reduced properly. Therefore, as the catalyst layer for fuelcells, a membrane electrode conjugate contained in the fuel cells hasinferior usefulness.

The catalyst of the present invention can be produced by supporting thecatalyst metal on the catalyst carrier. The method for supporting thecatalyst metal on the catalyst carrier is not particularly limited aslong as the supporting can be carried out practically. Particularly, itis preferred to employ a method for supporting the catalyst metal usinga precursor of the catalyst.

The precursor of the catalyst used herein is a substance capable ofbeing the above catalyst metal by a prescribed treatment, such asplatinic chloride, iridium chloride, silver nitrate or palladiumchloride.

The method of supporting the precursor of the catalyst on the catalystcarrier in not particularly limited, and a method of applying aconventionally known technique of supporting the catalyst metal can beused. Non-limiting examples are:

(1) a method comprising a step that the catalyst carrier is dispersed inthe catalyst precursor solution, dried and solidified by evaporation anda step of carrying out heat-treatment,(2) a method comprising a step that the catalyst carrier is dispersed inthe catalyst precursor colloidal solution, the catalyst precursorcolloid is adsorbed on the catalyst carrier and thereby the catalystmetal is supported on the catalyst carrier, and(3) a method comprising a step that the pH of a mixed solution of asolution containing one or more of the metal compounds which are rawmaterials for the catalyst precursor and the catalyst precursorcolloidal solution is regulated and thereby a metal oxide, awater-containing oxide and a metal hydroxide are prepared andsimultaneously the catalyst precursor colloid is adsorbed, and a step ofdrying thereof.

As the process for preparing the catalyst of the present invention, itis preferred to use the method (1) because the catalyst metal is highlydispersed and supported on the surface of the catalyst carrier and thedesired catalyst is prepared.

As the method of dispersing and supporting the catalyst metal on thecatalyst carrier by the steps of the method (1), it is possible toemploy a usual impregnation method.

The catalyst precursor solution may be obtainable through the abovesteps by the catalyst metal (may be a reside after the heat treatment).Non-limiting examples thereof are a platinic chloride aqueous solution,iridium chloride, silver nitride and palladium chloride.

Although the content of the catalyst precursor in the catalyst precursorsolution is not particularly limited, the content may be not higher thanthe saturation concentration. Nevertheless, the proper and necessaryconcentration is determined because when the concentration is low, it isnecessary for regulation of the concentration to repeat the above stepuntil the supported amount becomes the desired amount. The catalystprecursor solution has a catalyst precursor content, which is notlimited, of about 0.01 to 50% by mass.

One examples of the supporting method may include the following method.

A solution prepared by suspending the catalyst carrier in distilledwater is put on a hot plate and kept at a liquid temperature of 80° C.while stirring. The platinic chloride aqueous solution previouslyprepared is slowly added to the suspension over 30 min and aftercompletion of the dropping, the mixture is stirred at 80° C. for 2 hr.

Next, a formaldehyde aqueous solution (trade one: 37% by mass) is slowlyadded to the suspension and after completion of the addition, themixture is stirred at 80° C. for 1 hr.

After completion of the reaction, the suspension is cooled and filteredoff. The crystal filtered is heated in a nitrogen stream at 400° C. for2 hr, and thereby a platinum-supported carrier, which is the catalyst ofthe present invention, is prepared.

Meanwhile, the catalyst carrier and the platinic chloride are fullysuspended in water and filtered off, and then the collected solid isdried at room temperature. This solid is dried in a drying oven at 120°C. for 12 hr, and thereafter the solid is reduced while passing throughhydrogen with elevating the temperature to 350° C. for 2 hr to preparethe platinum-supported carrier, which is the carrier of the presentinvention.

<Use>

The catalyst of the present invention can be used as a catalyst for fuelcells, exhaust gas treatment or organic synthesis. As described above,the catalyst of the present invention can secure sufficiently largecatalytic ability without decreasing the particle diameter thereof, andhas excellent heat resistance. Particularly, the catalyst of the presentinvention is suitable for the catalyst for fuel cells.

The catalyst of the present invention can form a catalyst layer for fuelcells. Examples of the catalyst layer for fuel cells may include ananode catalyst layer and a cathode catalyst layer. The above catalystcan be used for any of the catalyst layers. Since the catalyst layer forfuel cells according to the present invention has high oxygen reducingability and contains the catalyst incapable of corroding in a highpotential in an acidic electrolyte, it is useful as a catalyst layer(catalyst layer for cathode) provided on a cathode of a fuel cell.Particularly, it is favorably used in the catalyst layer provided on thecathode of a membrane electrode conjugate, which is provided in thesolid polymer type fuel cells.

EXAMPLES

The present invention will be described in more detail with reference tothe following examples below, but it is not limited by these examples.

Various measurements in the examples and comparative examples arecarried out in the following methods.

[Analysis Methods] 1. Powder X Ray Diffraction

The powder X ray diffraction on a specimen was carried out using RotarFlex manufactured by Rigaku Corporation and a X′Pert-Pro manufactured byPANalytical.

The number of diffraction peaks in the powder X-ray diffraction of eachspecimen was determined by regarding a signal, which can be detected ina ratio (S/N) of signal (S) to noise (N) of 2 or more, as one peak.

The noise (N) was taken as a width of a base line.

2. Element Analysis

Carbon: About 0.1 g of a specimen was weighed and measured by EMIA-110manufactured by Horiba Ltd.Nitrogen and Oxygen: About 0.1 g of a specimen was weighed, put andsealed in Ni-Cup. Thereafter, the specimen was measured by an ONanalysis apparatus.Niobium: About 0.1 g of a specimen was weighed in a platinum pan andthermally decomposed by addition of nitric acid-hydrofluoric acid. Thisthermally decomposed material was determined volumetrically, diluted anddetermined by ICP-MS.

Example 1 1. Preparation of Catalyst Carrier

4.96 g (81 mmol) of niobium carbide, 1.25 g (10 mmol) of niobium oxideand 0.54 g (5 mmol) of niobium nitride were fully mixed and heated in anitrogen atmosphere at 1600° C. for 3 hr to prepare 2.70 g of niobiumcarbon nitride. The resulting sintered niobium carbon nitride waspulverized by a ball mill.

1.05 g of the niobium carbon nitride was heated in a tube-like furnacewhile feeding an argon gas containing 1% by volume of oxygen gas at 800°C. for 1 hr, and thereby 1.12 g of a niobium oxycarbonitride(hereinafter referred to “catalyst carrier (1)”) was prepared.

The powder X-ray diffraction spectrum of the resulting catalyst carrier(1) is shown in Table 1. At the diffraction angle 2θ in the range of 33°to 43°, four diffraction line peaks were observed. The element analysisresults of the catalyst carrier (1) are shown in Table 1.

TABLE 1 The element analysis results of the catalyst carrier (1) (wt %;the parenthetic number is an element ratio to Nb) Niobium carbon nitrideNb C N O Composition Example 1 76.5 4.69 4.28 8.98NbC_(0.53)N_(0.41)O_(0.76) NbC_(0.00)N_(0.49) (1)  (0.53) (0.41) (0.76)

In the element analysis of the resulting niobium oxycarbonitride, theniobium oxycarbonitride had a composition NbC_(x)N_(y)O_(z) in which x,y and Z were 0.53, 0.41 and 0.76 respectively in this order and thetotal of x, y and Z (X+Y+z) was 1.7.

2. Preparation of Catalyst (Method of Synthesizing a 10% by WeightPlatinum Catalyst)

0.900 g of the niobium oxycarbonitride (the pulverized one was used:particle diameter of 100 nm) was added to 100 ml of distilled water andshaken for 30 min by an ultrasonic cleaner.

The suspension was put on a hot plate and kept at a liquid temperatureof 80° C. with stirring. To the suspension, sodium carbide (0.172 g) wasadded.

To 50 ml of distilled water, 266 mg (0.513 mmol: 100 mg in terms of theplatinum amount) of platinic chloride (H₂PtCl₆.6H₂O) was dissolved toprepare a solution. The solution was slowly added to the suspension over30 min (the solution temperature was kept at 80° C.). After completionof the dropping, the suspension, as it is, was stirred at 80° C. for 2hr.

Next, 10 ml of a formaldehyde aqueous solution (trade one: 37%) wasslowly added to the suspension. After completion of the addition, thesuspension was stirred at 80° C. for 1 hr.

After completion of the reaction, the suspension was cooled and filteredoff. The crystal filtered was heated in a nitrogen stream at 400° C. for2 hr to prepare 850 mg of a 10% platinum-supported carrier (catalyst(1)).

The powder X-ray diffraction spectrum of the catalyst (1) is shown inFIG. 2. At the diffraction angle 2θ in the range of 33° to 43°, fourdiffraction line peaks were observed.

Furthermore, in the element analysis result of the catalyst (1), theamount of Pt was 8.5% by weight. The element analysis results of thecatalyst (1) are shown in Table 2.

Moreover, the SEM photograph of the platinum-supported carrier thatplatinum was supported on the niobium oxycarbonitride carrier is shownin FIG. 10.

TABLE 2 Nb Pt 0 N C Example 1 63.6 8.5 22.8 2.8 1.4 Example 2 78.3 2.37.4 6.1 3.9 (unit: % by weight)

3. Production of Electrode for Fuel Cells

0.095 g of the catalyst (1) and 0.005 g of carbon (XC-72 manufactured byCabot Co.) were fed to 10 g of a mixed solution having a weight ratio ofisopropyl alcohol to pure water of 2/1, stirred and suspended by anultrasonic wave to prepare a mixture. 30 μl of this mixture was appliedon a glassy carbon electrode (diameter: 5.2 mm manufactured by TokaiCarbon Co.) and dried at 120° C. for 1 hr. Furthermore, 10 μl of thediluted Nafion solution prepared by diluting Nafion (5% Nafion solution(DE521) manufactured by DuPont Co.) 10 times by pure water was appliedand dried at 120° C. for 1 hr to prepare an electrode for fuel cells(1).

4. Evaluation on Oxygen Reducing Ability

The catalytic ability (oxygen reducing ability) of the electrode (1) forfuel cells thus prepared was evaluated by the following method.

At first, the electrode (1) for fuel cells thus prepared was polarizedin an oxygen atmosphere and in a nitrogen atmosphere in a 0.5 mol/dm³sulfuric acid solution at 30° C. at a potential scanning rate of 5mV/sec and the current-potential curve was measured. In the measurement,a reversible hydrogen electrode having the same concentration in thesulfuric acid solution was used as a reference electrode.

From the measurement results, the potential at which the difference ofnot less than 0.2 μA/cm² begins to appear between the reducing currentin an oxygen atmosphere and the reducing current in a nitrogenatmosphere was taken a starting potential for oxygen reduction and thedifference of the both was taken as an oxygen reducing current.

The catalytic ability (oxygen reducing ability) was evaluated on theelectrode (1) for fuel cells prepared from this starting potential foroxygen reduction and the oxygen reducing current.

Namely, it shows that as the starting potential for oxygen reduction ishigher or the oxygen reducing current is larger, the catalytic ability(oxygen reducing ability) of the electrode (1) for fuel cells is higher.

The current-potential curve obtained from the above measurement is shownin FIG. 3.

The electrode (1) for fuel cells prepared in Example 1 was found to havea starting potential for oxygen reduction of 0.98 V (vs. NHE) and highoxygen reducing ability.

Example 2 1. Preparation of Catalyst (Method of Synthesizing a 2.5% byWeight Platinum Catalyst)

0.975 g of the niobium oxycarbonitride (the pulverized one was used:particle diameter of 100 nm) prepared in Example 1 was added to 100 mlof distilled water and shaken for 30 min by an ultrasonic cleaner. Thesuspension was put on a hot plate and kept at a liquid temperature of80° C. with stirring. To the suspension, sodium carbide (0.043 g) wasadded.

To 25 ml of distilled water, 67 mg (0.134 mmol: 25 mg in terms of theplatinum amount) of platinic chloride (H₂PtCl₆.6H₂O) was dissolved toprepare a solution. The solution was slowly added to the suspension over30 min (the solution temperature was kept at 80° C.). After completionof the dropping, the suspension, as it is, was stirred at 80° C. for 2hr.

Next, 5 ml of a formaldehyde aqueous solution (trade one: 37%) wasslowly added to the suspension. After completion of the addition, thesuspension, as it is, was stirred at 80° C. for 1 hr.

After completion of the reaction, the suspension was cooled and filteredoff. The crystal filtered was heated in a nitrogen stream at 400° C. for2 hr to prepare 800 mg of a 2.5% platinum-supported carrier (catalyst(2)).

The powder X-ray diffraction spectrum of the catalyst (2) is shown inFIG. 4. At a diffraction angle 2θ in the range of 33° to 43°, fourdiffraction line peaks were observed.

Furthermore, in the element analysis result of the catalyst (2), theamount of Pt was 2.3% by weight. The element analysis results of thecatalyst (2) are shown in Table 2.

2. Production of Electrode for Fuel Cells

0.095 g of the catalyst (2) and 0.005 g of carbon (XC-72 manufactured byCabot Co.) were fed to 10 g of a mixed solution having a weight ratio ofisopropyl alcohol to pure water of 2/1, stirred and suspended by anultrasonic wave to prepare a mixture. 30 μl of this mixture was appliedon a glassy carbon electrode (diameter: 5.2 mm manufactured by TokaiCarbon Co.) and dried at 120° C. for 1 hr. Furthermore, 10 μl of thediluted Nafion solution prepared by diluting Nafion (5% Nafion solution(DE521) manufactured by DuPont Co.) 10 times by pure water was appliedand dried at 120° C. for 1 hr to prepare an electrode (2) for fuelcells.

3. Evaluation on Oxygen Reducing Ability

The catalytic ability (oxygen reducing ability) of the electrode (2) forfuel cells thus prepared was evaluated by the following method.

At first, the electrode (2) for fuel cells thus prepared was polarizedin an oxygen atmosphere and in a nitrogen atmosphere in a 0.5 mol/dm³sulfuric acid solution at 30° C. at a potential scanning rate of 5mV/sec and the current-potential curve was measured. In the measurement,a reversible hydrogen electrode having the same concentration in thesulfuric acid solution was used as a reference electrode.

From the measurement results, the potential at which the difference ofnot less than 0.2 μA/cm2 begins to appear between the reducing currentin an oxygen atmosphere and the reducing current in a nitrogenatmosphere was taken as a starting potential for oxygen reduction andthe difference of the both was taken as an oxygen reducing current.

The catalyst ability (oxygen reducing ability) was evaluated on theelectrode (2) for fuel cells prepared from this starting potential foroxygen reduction and the oxygen reducing current.

Namely, it shows that as the starting potential for oxygen reduction ishigher or the oxygen reducing current is larger, the catalyst ability(oxygen reducing ability) of the electrode (2) for fuel cells is higher.

The current-potential curve prepared from the above measurement is shownin FIG. 5.

The electrode (2) for fuel cells prepared in Example 2 was found to havea starting potential for oxygen reduction of 0.95 V (vs. NHE) and highoxygen reducing ability.

Comparative Example 1

Using 55.8% Pt/C manufactured Wako Pure Chemical Industries Ltd. as acatalyst (3), an electrode (3) for fuel cells was prepared and theproduction of an electrode for fuel cells and the evaluation on theoxygen reducing ability were carried out in the same manner as inExample 1.

The current-potential curve prepared from the same measurement as in theexample is shown in FIG. 6.

The electrode (3) for fuel cells prepared in Comparative Example 1 wasfound to have a starting potential for oxygen reduction of 0.98 V (vs.NHE) and high oxygen reducing ability.

The SEM photograph of the platinum-supported carbon that platinum wassupported on the carbon carrier is shown in FIG. 11.

Comparative Example 2

Using 1% Pt/C manufactured Wako Pure Chemical Industries Ltd. as acatalyst (4), an electrode (4) for fuel cells was prepared and theproduction of an electrode for fuel cells and the evaluation on theoxygen reducing ability were carried out in the same manner as inExample 1.

The current-potential curve prepared from the same measurement as in theexample is shown in FIG. 7.

The electrode (4) for fuel cells prepared in Comparative Example 2 wasfound to have a starting potential for oxygen reduction of 0.87V (vs.NHE) and to have not so high oxygen reducing ability as a platinumsupported carrier.

Comparison Between the Examples and the Comparative Examples

The current-potential curves obtained in Examples 1 and 2 andComparative Examples 1 and 2 are inclusively shown in FIG. 8. In FIG. 8,A shows the current-potential curve obtained in Example 1 that 10%Pt/NbCNO was used, B shows the current-potential curve obtained inExample 2 that 2.5% Pt/NbCNO was used, C shows the current-potentialcurve obtained in Comparative Example 1 that 55.8% Pt/C was used and Dshows the current-potential curve obtained in Comparative Example 2 that1% Pt/C was used.

The comparison on the current density at 0.85V between theplatinum-supported NbCNO and the platinum-supported carbon prepared inExamples 1 and 2 and Comparative Examples 1 and 2 is shown in FIG. 9. InFIG. 9, A shows a straight line obtained from the measurement using theplatinum-supported NbCNO and B shows a straight line obtained from themeasurement using the platinum-supported carbon.

Example 3 1. Preparation of Catalyst Carrier

5.88 g (56 mmol) of niobium carbide, 0.87 g (5 mmol) of ferrous acetateand 5.14 g (48 mmol) of niobium nitride were fully mixed and heated in anitrogen atmosphere at 1600° C. for 3 hr to prepare 10.89 g of iron andniobium-containing carbon nitride. Since the resulting iron andniobium-containing carbon nitride was sintered one, it was pulverized bya ball mill.

1.00 g of the iron and niobium-containing carbon nitride washeat-treated in a tube-like furnace while feeding a nitrogen gascontaining 1% by volume of oxygen gas and 0.8% by volume of hydrogen gasat 900° C. for 6 hr, and thereby 1.24 g of a iron (5% by mole) andniobium-containing oxycarbonitride (hereinafter referred to “catalystcarrier (5)”) was prepared.

The powder X-ray diffraction spectrum of the resulting catalyst carrier(5) is shown in Table 12. The element analysis results of the catalystcarrier (5) are shown in Table 3.

TABLE 3 Example 3 Nb Fe C N O Composition NbFeC_(0.60)N_(0.49) 67.2 2.13.2 0.7 28.6 Nb_(0.95)Fe_(0.05)C_(0.35)N_(0.07)O_(2.2) (0.95) (0.05)(0.35) (0.07) (2.2) (unit: % by weight; the parenthetic number is anelement ratio to Nb)

In the element analysis of the resulting iron and niobium-containingcarbon nitride, the iron and niobium-containing oxycarbonitride had acomposition NbFeC_(x)N_(y)O_(z) in which x, y and Z were 0.35, 0.07 and2.2 respectively in this order and the total of x, y and Z (X+Y+z) was2.62.

2. Preparation of Catalyst (Method of Synthesizing a 10% by WeightPlatinum Catalyst)

0.900 g of the iron and niobium-containing oxycarbonitride (thepulverized one was used: particle diameter of 100 nm) was added to 100ml of distilled water and shaken for 30 min by an ultrasonic cleaner.The suspension was put on a hot plate and kept at a liquid temperatureof 80° C. with stirring. To the suspension, sodium carbide (0.172 g) wasadded.

To 50 ml of distilled water, 266 mg (0.513 mmol: 100 mg in terms of theplatinum amount) of platinic chloride (H₂PtCl₆.6H₂O) was dissolved toprepare a solution. The solution was slowly added to the suspension over30 min (the solution temperature was kept at 80° C.). After completionof the dropping, the suspension, as it is, was stirred at 80° C. for 2hr.

Next, 10 ml of a formaldehyde aqueous solution (trade one: 37%) wasslowly added to the suspension. After completion of the addition, thesuspension was stirred at 80° C. for 1 hr.

After completion of the reaction, the suspension was cooled and filteredoff. The crystal filtered was heated in a nitrogen stream at 400° C. for2 hr to prepare 846 mg of a 10% platinum-supported carrier (catalyst(5)).

Furthermore, in the element analysis results of the catalyst (5), theamount of Pt was 8.7% by weight. Using the catalyst (5), the productionof a fuel cell electrode and the evaluation of the oxygen reducingability were carried out in the same manner as in Example 1.

The current-potential curve prepared from the above measurement, whichwas carried out in the same manner as in Example 1, is shown in FIG. 13.

The electrode (5) for fuel cells prepared in Example 3 was found to havea starting potential for oxygen reduction of 1.01 V (vs. NHE) and highoxygen reducing ability.

Example 4 1. Preparation of Catalyst Carrier

5.88 g (56 mmol) of zirconium carbide and 5.14 g (48 mmol) of zirconiumnitride were fully mixed and heated in a nitrogen atmosphere at 1600° C.for 3 hr to prepare 10.89 g of zirconium-containing carbon nitride.Since the resulting zirconium-containing carbon nitride was sinteredone, it was pulverized by a ball mill.

1.00 g of the zirconium-containing carbon nitride was heat-treated in arotary kiln furnace while feeding a nitrogen gas containing 1% by volumeof oxygen gas and 2% by volume of hydrogen gas at 1200° C. for 12 hr,and thereby 1.24 g of a zirconium-containing oxycarbonitride(hereinafter referred to “catalyst carrier (6)”) was prepared.

The powder X-ray diffraction spectrum of the resulting catalyst carrier(6) is shown in FIG. 14.

2. Preparation of Catalyst (Method of Synthesizing a 10% by WeightPlatinum Catalyst)

0.900 g of the zirconium-containing oxycarbonitride (the pulverized onewas used: particle diameter of 100 nm) was added to 100 ml of distilledwater and shaken for 30 min by an ultrasonic cleaner. The suspension wasput on a hot plate and kept at a liquid temperature of 80° C. withstirring. To the suspension, sodium carbide (0.172 g) was added.

To 50 ml of distilled water, 266 mg (0.513 mmol: 100 mg in terms of theplatinum amount) of platinic chloride (H₂PtCl₆.6H₂O) was dissolved toprepare a solution. The solution was slowly added to the suspension over30 min (the solution temperature was kept at 80° C.). After completionof the dropping, the suspension, as it is, was stirred at 80° C. for 2hr.

Next, 10 ml of a formaldehyde aqueous solution (trade one: 37%) wasslowly added to the suspension. After completion of the addition, thesuspension, as it is, was stirred at 80° C. for 1 hr.

After completion of the reaction, the suspension was cooled and filteredoff. The crystal filtered was heated in a nitrogen stream at 400° C. for2 hr to prepare 828 mg of a 10% platinum-supported carrier (catalyst(6)).

Furthermore, in the element analysis results of the catalyst (6), theamount of Pt was 8.5% by weight. Using the catalyst (6), the productionof a fuel cell electrode and the evaluation of the oxygen reducingability were carried out in the same manner as in Example 1.

The current-potential curve prepared from the above measurement, whichwas carried out in the same manner as in Example 1, is shown in FIG. 15.

The electrode (6) for fuel cells prepared in Example 4 was found to havea starting potential for oxygen reduction of 0.98 V (vs. NHE) and highoxygen reducing ability.

Example 5 1. Preparation of Catalyst Carrier

5.10 g (85 mmol) of titanium carbide, 0.80 g (10 mmol) of titanium oxide(TiO₂) and 0.31 g (5 mmol) of titanium nitride (TiN) were fully mixedand heated in a nitrogen atmosphere at 1800° C. for 3 hr to prepare 5.73g of titanium carbon nitride. Since the resulting titanium carbonnitride was sintered one, it was pulverized by an automatic mortar.

1.00 g of the titanium-containing carbon nitride was heated in atube-like furnace while feeding a nitrogen gas containing 1% by volumeof oxygen gas and 4% by volume of hydrogen gas at 1000° C. for 10 hr,and thereby 1.31 g of a titanium-containing oxycarbonitride (hereinafterreferred to “catalyst carrier (7)”) was prepared.

The powder X-ray diffraction spectrum of the resulting catalyst carrier(7) is shown in FIG. 16. The element analysis results of the catalystcarrier (7) are shown in Table 4.

TABLE 4 Example 5 Ti C N 0 Composition TiC_(0.60)N_(0.50) 61.7 2.03 0.6235.88 TiC_(0.13) N_(0.03)O_(1.74) (1)  (0.13) (0.03) (1.74) (unit: wt %;the parenthetic number is an element ratio to Nb)

In the element analysis of the resulting titanium-containingoxycarbonitride, the titanium-containing oxycarbonitride had acomposition TiC_(x)N_(y)O_(z) in which x, y and Z were 0.13, 0.03 and1.74 respectively in this order and the total of x, y and Z (X+Y+z) was1.9.

2. Preparation of Catalyst (Method of Synthesizing a 10% by WeightPlatinum Catalyst)

0.900 g of the titanium-containing oxycarbonitride (the pulverized onewas used: particle diameter of 100 nm) was added to 100 ml of distilledwater and shaken for 30 min by an ultrasonic cleaner. The suspension wasput on a hot plate and kept at a liquid temperature of 80° C. withstirring. To the suspension, sodium carbide (0.172 g) was added.

To 50 ml of distilled water, 133 mg (0.256 mmol: 50 mg in terms of theplatinum amount) of platinic chloride (H₂PtCl₆.6H₂O) was dissolved toprepare a solution. The solution was slowly added to the suspension over30 min (the solution temperature was kept at 80° C.). After completionof the dropping, the suspension, as it is, was stirred at 80° C. for 2hr.

Next, 5 ml of a formaldehyde aqueous solution (trade one: 37%) wasslowly added to the suspension. After completion of the addition, thesuspension, as it is, was stirred at 80° C. for 1 hr.

After completion of the reaction, the suspension was cooled and filteredoff. The crystal filtered was heated in a nitrogen stream at 400° C. for2 hr to prepare 799 mg of a 5% platinum-supported carrier (catalyst(7)).

Furthermore, in the element analysis results of the catalyst (7), theamount of Pt was 4.4% by weight. Using the catalyst (7), the productionof a fuel cell electrode and the evaluation of the oxygen reducingability were carried out in the same manner as in Example 1.

The current-potential curve prepared from the above measurement, whichwas carried out in the same manner as in Example 1, is shown in FIG. 17.

The electrode (7) for fuel cells prepared in Example 5 was found to havea starting potential for oxygen reduction of 1.00 V (vs. NHE) and highoxygen reducing ability.

POSSIBILITY OF INDUSTRIAL USE

The catalyst carrier of the present invention has excellent heatresistance and can attain high catalyst ability without increasing thespecific surface area thereof. Accordingly, the catalyst carrier can befavorably used for various catalysts, particularly catalysts for fuelcells.

1. A catalyst carrier comprising a metal oxycarbonitride, wherein the metal oxycarbonitride has a composition represented by MC_(x)N_(y)O_(z) in which M is at least one metal selected from the group consisting of niobium, tin, indium, tantalum, zirconium, copper, iron, chromium, hafnium, titanium, vanadium, cobalt, manganese, cerium, mercury, plutonium, gold, silver, palladium, yttrium, lanthanum, praseodymium, neodymium, promethium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, and nickel, x, y and z are each a proportion of each atomic number and satisfy 0.01≦x≦2, 0.01≦y≦2, 0.01≦z≦3 and 1.7≦x+y+z≦5.
 2. A catalyst carrier comprising a metal oxycarbonitride, wherein the metal oxycarbonitride has a composition represented by MC_(x)N_(y)O_(z) in which M is at least one metal selected from the group consisting of niobium, tantalum, zirconium, hafnium, titanium and vanadium, x, y and z are each a proportion of each atomic number and satisfy 0.01≦x≦2, 0.01≦y≦2, 0.01≦z≦3 and 1.7≦x+y+z≦5.
 3. A catalyst carrier comprising a metal oxycarbonitride, wherein the metal oxycarbonitride has a composition represented by MC_(x)N_(y)O_(z) in which M is at least one metal selected from the group consisting of niobium, tantalum, zirconium, hafnium, titanium and vanadium, x, y and z are each a proportion of each atomic number and satisfy 0.01≦x≦2, 0.01≦y≦2, 0.01≦z≦3 and 1.7≦x+y+z≦5.
 4. An ink for producing a catalyst layer for a fuel cell produced by dispersing, in a solvent, a catalyst comprising the catalyst carrier as claimed in claim 1 and a catalyst metal supported on the catalyst carrier.
 5. A catalyst layer for a fuel cell comprising a catalyst comprising the catalyst carrier as claimed in claim 1 and a catalyst metal supported on the catalyst carrier.
 6. An electrode for a fuel cell having the catalyst layer for a fuel cell as claimed in claim
 5. 7. A membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer and a polymer electrolyte membrane arranged between the cathode catalyst layer and the anode catalyst layer, wherein the cathode catalyst layer and/or the anode catalyst layer is the catalyst layer for a fuel cell as claimed in claim
 5. 8. A fuel cell having the membrane electrode assembly as claimed in claim
 7. 9. An ink for producing a catalyst layer for a fuel cell produced by dispersing, in a solvent, a catalyst comprising the catalyst carrier as claimed in claim 2 and a catalyst metal supported on the catalyst carrier.
 10. An ink for producing a catalyst layer for a fuel cell produced by dispersing, in a solvent, a catalyst comprising the catalyst carrier as claimed in claim 3 and a catalyst metal supported on the catalyst carrier.
 11. A catalyst layer for a fuel cell comprising a catalyst comprising the catalyst carrier as claimed in claim 2 and a catalyst metal supported on the catalyst carrier.
 12. A catalyst layer for a fuel cell comprising a catalyst comprising the catalyst carrier as claimed in claim 3 and a catalyst metal supported on the catalyst carrier.
 13. An electrode for a fuel cell having the catalyst layer for a fuel cell as claimed in claim
 11. 14. An electrode for a fuel cell having the catalyst layer for a fuel cell as claimed in claim
 12. 15. A membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer and a polymer electrolyte membrane arranged between the cathode catalyst layer and the anode catalyst layer, wherein the cathode catalyst layer and/or the anode catalyst layer is the catalyst layer for a fuel cell as claimed in claim
 11. 16. A membrane electrode assembly comprising a cathode catalyst layer, an anode catalyst layer and a polymer electrolyte membrane arranged between the cathode catalyst layer and the anode catalyst layer, wherein the cathode catalyst layer and/or the anode catalyst layer is the catalyst layer for a fuel cell as claimed in claim
 12. 17. A fuel cell having the membrane electrode assembly as claimed in claim
 15. 18. A fuel cell having the membrane electrode assembly as claimed in claim
 16. 